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6.thermodynamics AK 2018-19
6.thermodynamics AK 2018-19
2018-2019
Class: 11 Worksheet Number:11/Chem/06/AK
Subject: Chemistry Chapter 06:Thermodynamics
Section A
Each question carries 1 mark :
1. Give the mathematical expression of first law of thermodynamics.
∆U = q + w
Where ∆U = change in internal energy
q = heat absorbed or released
w = work done by the system or on the system
2. Derive the mathematical expression for 1st law of thermodynamics and state its limitations.
First law of Thermodynamics:
Let a system having internal energy ‘u’ absorb certain amount of energy ‘q’
Internal Energy = q + U1
If work done is ‘w’ on it, Internal Energy becomes ‘U2’
U2 = U1 + q +w
U2 - U1 = q +w
ΔU = q+w
23. Entropy of diamond is less than that of graphite. What conclusion do you draw from this?
Less entropy means less disorder i.e., all the Carbon atoms are linked to form a network structure.
Greater entropy of graphite implies some disorder which is due to presence of free electrons and
slipping of layers over each other.
In diamond each carbon atom undergoes sp3 hybridisation and linked to four other carbon atoms
by using hybridised orbitals in tetrahedral fashion. The structure extends in space and produces a
rigid three-dimensional network of carbon atoms. It is very difficult to break extended covalent
bonding and, therefore, diamond is a hardest substance on the earth it implies less entropy in
diamond.
Graphite has a layered structure held by van der Waal’s forces, each C atom undergoes
sp2hybridisation and will make 3 sigma bond with 3 neighbouring C atom the fourth electron
forms a pi bond and the electrons are mobile which implies more entropy in graphite.
24. Define entropy and free energy. How are they related to each other?
Entropy is the measure of the randomness or disorderliness of the system.
Whereas, free energy of a system is its capacity to do useful work.
They are related by Gibbs’s Helmholtz equation
∆G = ∆H –T∆S
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25. Explain why the entropy of a pure crystalline substance is zero at 0 K? State the law on which it
is based. Give the application of this law?
At 0 K, there is a perfectly ordered arrangement of the constituent particles of a pure crystalline
substance and there is no disorder at all. Hence its entropy is taken a zero.
This statement is based on the third law of thermodynamics.
The law is applied to findthe absolute entropy of a substance in any state at any temperature.
Section B
Each question carries 1 mark :
26. What would be the work done on / by the system if the internal energy of the system falls by 200
J even when 100 J of heat is supplied to it?
ΔU = -200 J ; q = 100 J
ΔU = q + w
-200 = 100 + w
-100 -200 = w
W= -300j
27. DH Alone cannot be the sole criterion for the spontaneity of a reaction. Explain.
∆G = ∆H - T∆S
If ∆G = -ve (spontaneous)
∆G = 0 (equilibrium)
∆G = +ve (non-spontaneous)
28. Predict in which of the following, entropy increases/decreases
(i)A liquid crystallizes into a solid
(ii)Temperature of a crystalline solid is raised from 0 K to 115 K.
(i)After freezing, the molecules attain an ordered state and therefore, entropy decreases.
(ii)At 0 K, the contituent particles are static and entropy is minimum. If temperature is raised to
115 K, these begin to move and oscillate about their equilibrium positions in the lattice and
system becomes more disordered, therefore entropy increases.
29. What do you understand by spontaneity?
A reaction is said to be spontaneous if it occurs without being driven by some outside force.
30. If ΔG0 for a reversible reaction is found to be zero, what is the value of its equilibrium constant?
ΔG0= -2.303 RT log Kc
ΔG0 = 0, Kc =1
31. Calculate the entropy change involved in conversion of one mole (18 g) of solid ice at 273 K to
liquid water at the same temperature (latent heat of fusion = 6025 j mol-1 )
Entropy change for ice →water is given by
∆f S = ∆f H = 6025 =22.1 Jk-1mol-1
Tf273
Each question carries 2 marks :
32. In a process, 701 J of heat is absorbed by a system and 394 J of work is done by the system. What
is the change in internal energy for the process?
The first law of thermodynamics states that : ΔU = q + W (i)
Where,
ΔU = change in internal energy for a process
q = heat
W = work
Given in the question,
q = + 701 J (Positive since heat is absorbed)
W = –394 J (Negative since work is done by the system)
Substituting the values in equation (i), we get
ΔU = 701 J + (–394 J)
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ΔU = 307 J
Therefore, the change in internal energy for the process is 307 J.
33. Two moles of an ideal gas initially at 27oC and one atmospheric pressure are compressed
isothermally and reversibly till the final pressure of the gas is 10 atm. Calculate q, w and U for
the process.
n=2, R= 8.314 jk-1mol-1;T=(27 +273) = 300K
W max= 2.303 nRT log 10 p1/p2
= 2.303 x 2 x 8.314 x 300 x log 10/1
= 11488j
ΔU = q + w
The condition is isothermal and reversible ΔT= 0;ΔU=0
0 = q +W
-q =w
q= -11488j ; w = 11488j ;ΔU=0
34. A gas absorbs 120 J of heat and expands against external pressure 1.1 atm from volume of 0.5 L
to 2.0 L. Whatis the change in internal energy?
W = -PΔV = -1.1 X (2 – 0.5)
=-1.1 X 1.5 = -1.65 L-atm
1L-atm = 101.3 J
-1.65 L-atm = -167.145 j
ΔU = q + w
= 120 + (-167.145)
= -47.145 J
35.
Enthalpy of combustion of carbon to CO2 is –393.5 kJ mol–1. Calculate the heat released upon
formation of 35.2 g of CO2 from carbon and dioxygen gas?
36. Given
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37. Enthalpy of combustion of carbon to CO2 is –393.5 kJ mol–1. Calculate the heat released upon
formation of 35.2 g of CO2 from carbon and dioxygen gas?
38. The heat liberated on complete combustion of 7.8 g benzene is 327 kJ. The heat has been
measured at constant volume at 270 C. Calculate the heat of combustion of benzene at constant
pressure. ( R= 8.314 JK-1mol-1 )
When 7.8 gm of C6H6 is burnt heat = qv=∆U=327 kj
R= 8.314 kj k-1 mol-1∆H =?
∆H = ∆U + ∆ngRT
∆n = ∑ n of products (g) - ∑ n of reactant (g)
∆n = (6 + 0) – (0 + 15/2)
= 6 – 7.5
= - 1.5
1 mole of C6H6 = 78gm
∆U= -327 x 103 J/mol
∆H = ∆U + ∆nRT
∆H =-327 x 103 -(-1.5) (8.314) (300)
∆H = -327000– 3741.3
= - 3,30,741.3J
39. Calculate the enthalpy of formation of HF on the basis of the following data :
Bond energy of H-H = 434 kJ/mol
Bond energy of F-F = 158 kJ/mol
Bond Energy of H-F= 565 kJ/mol
H-H + F-F → 2 H-F
ΔH = ∑ B.E (reactant )- ∑ B.E (product)
= (434 + 158) – (2 x 565)
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=592 -1130
= -538 kj for 2 moles of HF
= -538/2 = -269 KJ/mol
40. Calculate the bond enthalpy of Cl – Cl bond from the following data :
CH 4 ( g ) Cl 2 ( g ) CH 3Cl ( g ) HCl( g ) DH 100.3kJ mol 1
.
Also the bond enthalpies of C – H, C – Cl and H – Cl bonds are 413, 326 and 431 kJ mol-1
respectively.
CH4 (g) + Cl2 (g) CH3Cl (g) +HCl (g) ΔH = - 100.3 kj/ mol
B.E. of C-H = 413 kj/ mol
B.E. of C-Cl = 326 kj/ mol
B.E. of H-Cl = 431 kj/ mol
B.E. of Cl-Cl= ?
Let B.E. of Cl-Cl bond be X kj/ mol
ΔH = ∑ B.E. (R) - ∑ B.E. (P)
100.3 = (413 x 4 x X) - (431 + 431 x 3 + 326)
-100.3 = 1652 + X – 1996
X = -100.3 – 1652 + 1996
X = 243.7 kj/ mol
41. Calculate the ΔrH0 for the reaction
H2(g) + Br2(g) 2HBr(g)
Bond enthalpy are given as : H – H = 436 kJ mol-1, Br – Br = 192 kJ mol-1,
H – Br =368 kJ mol-1
H2 (g) + Br2 (g) 2 HBr(g)
B.E. OF H-H = 436 kj/ mol; Br- Br = 192 kj/ mol, H-Br = 368 kj/ mol-1
ΔH = ∑ B.E. (Reactants) - ∑ B.E. (Products)
= (436 + 192) – (368 x 2)
= (436 + 192) – (736)
ΔH = -108 kj/ mol
42. Calculate the enthalpy change for the process
CCl4(g) → C(g) + 4Cl(g)
And calculate bond enthalpy of C–Cl in CCl4(g).
ΔvapHθ(CCl4) = 30.5 kJ mol–1.
ΔfHθ (CCl4) = –135.5 kJ mol–1.
ΔaHθ (C) = 715.0 kJ mol–1, where ΔaHθ is enthalpy of atomisation
ΔaHθ (Cl2) = 242 kJ mol–1
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43. Calculate the enthalpy of formation of benzoic acid (C6H5COOH(l)) from the following data :
ΔfH of CO2(g) = --393.5 kJ mol-1, ΔfH of H2O(l) = --285.8 kJ mol-1 ,
ΔcHof C6H5COOH(l) = --3227 kJ mol-1 .
C6H5COOH(l) + 15/2 O2 (g) 7CO2 (g) + 3H2O (l)
ΔrH = ∑ ΔfH (Products) - ∑ ΔfH (Reactants)
-3227 = 7 x (-393.5) + 3 x (-285.8) - ΔfH C6H5COOH(l) + 15/2 x O2
-3227 = - 2754.5 – 857.4 – x + 15/2(0)
x = - 2754.5 – 857.4 + 3227
x = -384.9 kj/ mol
44. Calculate the enthalpy of formation of benzene (C6H6) from the following data :
ΔfH of CO2(g) = -393.5 kJ mol-1, ΔfH of H2O(l) = -285.8 kJ mol-1 ,
ΔcH of C6H6 (l) = -3266 kJ mol-1
45. Find out the value of equilibrium constant for the following reaction at 298 K.
46. Enthalpy and entropy changes of areaction are 40.63˚kJ mol-1 and 108.8 JK-1 mol-1respectively.
Predict the feasibility of the reaction at 27˚ C.
∆H =40.63˚kJ=40630 Jmol-1,T =27 + 273 =300K
∆G = ∆H - T∆S
= 40630 – 300x108.8
= 7990 Jmol-1
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As ∆G value is positive the reaction will not be spontaneous and feasible.
47. For the reaction at 298 K, 2A + B C
ΔH = 400 kJ mol-1 and ΔS = 200 JK-1 mol-1.
At what temperature will the reaction become spontaneous?
48. Calculate ΔG0 for the reaction, N 2 ( g ) 3H 2 ( g ) 2 NH 3 ( g ) at 298 K. The value of Kc for
the reaction is 6.6 × 105. [ R = 8.314 JK-1mol-1 ]
N 2 ( g ) 3H 2 ( g ) 2 NH 3 ( g )
ΔG = -2.303 RT Log Kc
= -2.303 X 8.314 X 298 X Log 6.6 X 10 5
= 33205.13J/mol = 33.205 kj/mol
49. Calculate DS involved in the fusion of 3.6 g of ice at 00C. Latent heat of ice is 334.72J g-1.
∆f S = ∆f H = 334.72 x 3.6/273 = 4.41 J/K
Tf
50. Calculate DS 0 for a reaction X Y, if the value of DH 0 = 28.40 kJ mol-1 and Kc is 1.8 × 10—
7
at 298 K.
X Y
ΔG = -2.303 RTLogKc
= -2.303 x 8.314 x 10 -3 x 298 x log 1.8 x 10 -7
= 38.4842 kj/mol
ΔG = ΔH – TΔS
38.4842 kj/mol = 28.40 -298 x ΔS
ΔS = - 0.03383kj/K
51. Calculate the entropy change in surroundings when 1.00 mol of H2O (l) is formed under standard
conditions. Δf H0 = –286 kJ mol–1.
52. The equilibrium constant for a reaction is 10. What will be the value of ΔG0 ? R = 8.314 JK–1mol–
1
, T = 300 K.
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Section C
Each question carries 1 mark :
53. Does an aqueous solution of Mg2+ ions have larger entropy before or after hydration of ions?
Hydration is the term used for attachment of water molecules to ions when an ionic compound is
dissolved in water. It is a special case of dissolution of energy, with the solvent being water.
Before hydration an aqueous solution of Mg2+ ions will have larger entropy as after hydration
Mg2+ has achieved an orderly lattice.
54. For a reaction there is an increase in both enthalpy and entropy. Under what conditions does the
reaction occur spontaneously?
∆G = ∆H - T∆S
∆H =+ve and ∆S =+ve .At high temperature T∆S>∆H
∆G = -ve and spontaneous.
55. Dissolution of NH4Cl (s) in water is endothermic but it is spontaneous. Explain.
NH4Cl(s) + H2O → NH4+(aq) + Cl-(aq)
∆G = ∆H –T∆S ; as the number of particles are increasing after the dissolution of NH 4Cl as it
ionizes ∆s becomes +ve and –T∆ S overweighs +ve ∆H factor, so ∆G=-ve, reaction becomes
spontaneous.
Since the entropy of system increases therefore the process becomes spontaneous.
56. Lifting of water to the top of a hill is quite possible. Why can’t this be considered as a
spontaneous process?
Because it does not happen on its own and it will immediately stop once the initiation from the
motor stops .Therefore it is a non-spontaneous process.
57. For the reaction,
2Cl(g) → Cl2(g), what are the signs of ΔH and ΔS ?
ΔH and ΔS are negative
-875 = 2x (-393.5) + 2x(-285.8) –ΔfH of CH3COOH(l) -2 ΔfH O2x 0(as oxygen is in its
standard rate)
-875 =-787 – 571.6 -∆f H CH3COOH
X = -787 -571.6 + 875
X = -483.6 kj/mol
61. Comment on the thermodynamic stability of NO(g), given
½ N2(g) + ½ O2(g) → NO(g) ; ΔrHθ = 90 kJ mol–1
NO(g) + ½ O2(g) → NO2(g) : ΔrHθ= –74 kJ mol–1
63. The enthalpy change for the transition of liquid water to steam is 40.8 KJ mol -1 AT 373
k.Calculate ΔS° for the process.
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65. For the oxidation of iron, 4Fe (s) + 3O2(g) 2Fe2O3(s), entropy change is –549.4 JK-1 mol-1 at
298 K. Inspite of negative entropy change of this reaction, why is the reaction spontaneous?
ΔrH = --1648 × 103 J mol-1 , R = 8.314 JK-1 mol-1
66. Calculate ΔrG0 for conversion of oxygen to ozone, 3/2 O2(g) → O3(g) at 298 K. if Kpfor this
conversion is 2.47 × 10–29.
68. Both ethane and methane are used as fuel. Predict which of these is a better fuel? Given that heat
of formation of CH4 (g), C2H6 (g), CO2 (g) and H2O (l) are -74.85, -84.68, -393.5 and -286 kJ
mol-1 respectively.
CH4 (g) + 2O2 (g) → CO2(g) + 2 H2O(l)
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